Copper containing disazo dyestuffs



United States Patent Ofiice 3,227,705 Patented Jan. 4, 1966 This invention relates to new azo dyestuffs, and more particularly it relates to new copper-containing azo dyestuifs which are valuable for colouring textile materials, in particular-cellulose textile materials.

According to the invention there are provided the copper-containing azo dyestufis which, -in the form of the free acids, are represented by-the formula:

wherein A represents a sulphophenyl or sulphonaphthyl radical, Z represents a hydrogen atom or a methyl radical, n and In each independently represent 1 or 2, and L, which is attached to the 6-, 7- or 8 position of the naphthalene nucleus, represents a group of the formula:

wherein Y Y and Y each independently represent a hydrogen or a chlorine atom, and p represents 1 or 2.

It is however preferred that Y Y and Y each represent a hydrogen atom.

As examples of the sulphophenyl radicals represented by A there maybe mentioned 2-, 3- or 4-sulphophenyl and 2:5-, 3:5- or 2:4-disulp'hophenyl radicals; and as examples of the sulphonaphthyl radicals represented by A there may be mentioned 1-sulphonaphth-2-yl, 155-, 3:6-, 4:8- or 5:7-disulpho-naphth-2-yl, 4-, '5- or 6- sulphonaphthJ-y-l and 6- or -8-su'lphona-phth-2-yl radicals.

According to a further feature of the invention there is provided a process for the manufacture .of the copper-containing azo dyestuffs, as hereinbefore-defined, which comprises treating an azo compound which, in the form of the free acid, is represented by the formula:

(Formula I wherein A, Z and n have the meanings stated, X represents a methoxy, hydroxy or carboxylic acid group, and L which is attached to the 6-, 7- or 8-position of the naphthalene nucleus represents a group of the formula:

sIOaH wherein p represents 1 or 2, with a coppering agent and with an acylating agent derived from an acid of the formula:

I HOOC.C=C/

(Formula II) In carrying out the process of the invention the azo compound of Formula I can either be treated with the coppering agent and the resulting copper-containing azo compound of the for-mula:

(Formula 111) wherein A, Z, L m and n have the meanings stated, treated with the acid acylating agent; or the azo compound of Formula I can be treated with the said acylating agent to give an azo compound .of the formula:

(Formula IV) wherein A, L, X, Z and n have the meanings stated, which is subsequently treated with the coppering agent.

The treatment of the azo compounds of Formula Ior Formula IV with the coppering agent can be conveniently carried out by heating an aqueous solution containing the azo compound and the coppering agent; the copper-complexes so obtained can then be isolated by conventional methods. I

As examples of coppering agents there may be mentioned copper sulphate, copper acetate and cuprammonium sulphate.

The treatment of the azo compound of Formula I or of the copper-containing azo compound of Formula III with the said acylating agent can be conveniently brought about by adding the acylating agent to an aqueous solution of the said azo compound or of the said copper-containing azo compound, stirring the resulting mixture, preferably at a temperature between 0 and 20 (1., and if desired maintaining the pH of the mixture between 5.0 and 7.0 by the addition of an acid-binding agent such as sodium carbonate. The resulting acyl derivative can then be isolated by conventional methods.

As examples of the said acylating .agents there may be mentioned 01- or p chloro-acryloyl chloride, MLBIfl-tllClllO- roacryloyl chlorideand, above all, acryloyl chloride.

The azo compounds of 'Formula I may themselves be obtained bydiazotising an amine of the formula: A-NH wherein A has the meaning stated, coupling the resulting diazo compound with a para-coupling amine of the formula:

(Formula V) wherein X and Z have the meanings stated, or with the corresponding N-methane-w-sulphonate, if necessary hydrolysing off the N-methane-w-sulphonate group, re-di- (S 311) n (Formula VI) wherein L and n have the meanings stated.

As examples of the amines of the formula: ANH there may be mentioned aniline-2-, 3- or 4-sulphonic acid, aniline-2:4-, 2:5- or 3:5-disulphonic acid, l-naphthyl- -amine-4-, 5-, 6- or 7-sulphonic acid, 2-naphthylamine-l-, 6- or 8-sulphonic acid, 2-naphtl1ylamine-1:5-, 326-, 4:8-, 5:7- or 6:8-disulphonic acid and 2-naphthylamine-l:5:7 trisulphonic acid.

As examples of the para-coupling amines of Formula V there may be mentioned anthranilic acid, Z-anisidine and 2-methoxy-S-methylaniline.

As examples of the aminonaphthols of Formula VI there may be mentioned 6-amino-l-naphthol-3:S-disulphonic acid, 7-amino-l-naphthol-3:6-disulphonic acid, 6- (4'-amino-3'-sulphophenylamino)-l-naphthol 3:5-disulphonic acid, 7-(4-amino-3-sulphophenylamino)-l-naphthol-3 :6-disul-phonic acid, 8-amino-lnaphthol-3 6-disulphonic acid, 8-amino-l-naphthol-3:S-disulphonic acid, 8- amino-l-naphthol-S-sulphonic acid, 7-amino-l-naphthol- 3-sulphonic acid, 6-amino-l-naphthol-3-sulphonic acid, 8- (4'-amino-3'-sulphophenylamino)l-naphthol 3 :6 disulphonic acid, 7-(4-amino-3-sulphophenylamino)-l-naphthol-3-sulphonic acid and 6-(4'-a-mino-3'-sulphophenylamino)-l-naphthol-3 -sulphonic acid.

Alternatively the azo compounds of Formula IV can be obtained by coupling a diazotised amine of the formula: A-NH with a para-coupling amine of Formula V, rediazotising and coupling with an acylated aminonaphthol of the formula:

(Formula VII) SOaH wherein A, Z, Y Y and Y have the meanings stated.

A second preferred class of the copper-containing azo dyestuffs of the invention are the dyestuffs which, in the form of the free acids, are represented by the formula:

sOaH

SOzH

4 wherein A, Z, Y Y and Y have the meanings stated.

In these preferred classes it is further preferred that Y Y and Y each represent hydrogen atoms.

The copper-containing azo dyestuffs of the invention are valuable for colouring natural and artificial textile materials for example textile materials comprising cotton, viscose rayon, regenerated cellulose, wool, silk, polyamides and modified polyarcylonitrile fibres. For this purpose the dyestuffs can be applied to the textile materials by dyeing, padding or printing using in the latter case printing pastes containing the conventional thickening agents or oil-in-water emulsions or water-in-oil emulsions, whereby the textile materials are coloured in a wide variety of shades possessing excellent fastness to washing, perspiration, hypochlorite bleach (fastness to chlorine), acid treatments and to light. The said dyestuffs also build-up well on textile materials to give heavy depths of shade.

The copper-containing azo dyestuffs are particularly valuable as reactive dyestuffs for colouring cellulose textile materials. For this purpose the dyestuffs are preferably applied to the cellulose textile material in c0njunction with a. treatment with an alkaline agent, for example sodium carbonate or bicarbonate, sodium metasilicate, trisodium phosphate or sodium hydroxide which may be applied to the cellulose textile material before, during or after the application of the dyestuff. Alternatively when the dyed textile material is subsequently heated or steamed a substance such as sodium trichloroacetate, which becomes alkaline on heating or steaming, can be used.

The copper-containing azo dyestuffs of the invention can also be used for colouring nitrogen-containing textile materials, for example polyamide textile materials but, more particularly, woolen textile materials.

The copper-containing azo dyestuffs of the invention can be applied to nitrogen-containing textile materials from a mildly alkaline, neutral or acid dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that is to say the pH of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process by the addition of acids or acid salts or alkalis or alkaline salts. For example dyeing may be started at a dyebath pH of about 3.5 to 5.5 and raised during the dyeing process to about 6.5 to 7.5 or higher if desired. The dyebath may also contain substances which are commonly used in the dyeing of nitrogen-containing textile materials. As examples of such substances there may be mentioned ammonium acetate, sodium sulphate, ethyl tartrate, non-ionic dispersing agents such as condensates of ethylene oxide with amines, fatty alcohols or phenols, surface-active cationic agents such as quaternary ammonium salts for example cetyl trimethylammonium bromide and cetyl pyridinium bromide and organic liquids such as n-butanol and benzyl alcohol.

When so applied to woollen textile materials the dyestuffs possess good fastness to Washing, milling, wet heat setting treatments and to light.

The invention is illustrated but not limited by the following examples in which the parts and percentages are by weight.

Example 1 Diazotised aniline-2:5-disulphonic acid is coupled with 2-methoxy-5-methylaniline, the aminoazo compound so obtained is diabotised and coupled under alkaline conditions with an equimolecular proportion of 6-atnino-1-naphthol-3z5-disulphonic acid and the aminodisazo compound so obtained is converted to its copper complex by heating it for 20 hours at a temperature between 95 and 100 C. with an aqueous solution of cuprammonium sulphate.

A solution of 86.7 parts of the tetra-sodium salt of 5 aqueous solution of sodium carbonate is simultaneously added to maintain the pH of the resulting mixture between 5.5 and 6.5. The mixture is then stirred for 18 hours at 20 (3., 170 parts of sodium chloride are added and the copper-containing azo dyestufi is filtered off and dried.

The following table gives further examples of coppercontaining azo dyestuffs of the invention which are obtained when the azo compounds, which are themselves obtained by diazotising the amines listed in the second column of the table, coupling with the para-coupling amines listed in the third column of the table, rediazotising and coupling with the aminonaphthols listed in the fourth column of the table, are treated with a coppering agent and with the acylating agents listed in the fifth column of the table by methods similar to those described in Example 1. The sixth column of the table indicates the shades obtained when the said dyestuflFs are applied to cellulose textile materials in conjunction with a treatment with an acid- When applied to cellulose textile materials in conjunc- 15 binding agent.

Example Amine Para-coupling amine Aminonaphthol Acylating agent Shade 4. Aniline-2:5-disulph0nic acid- 2-methoxy-5-methyIaniline 6-amino-1-naphthol-3:5- fl-Chloroacryloyl chloride. Blue.

disulphonic acid.

5 do do do azBzB-Trichloroacryloyl D0.

chloride.

6 dn dn 7-(4'-amino-3'-sulphophen- Acryloyl bromide Grey.

ylamino) -1-uaphthol-3- sulphonic acid.

7 do -do do a-Ohloroaeryloyl chloride".-- D0.

8 Orthanilie aei rl -do 8-amin0-1-naphth ol-3z6- Acryloyl chloride Blue.

disulphonic acid.

tion with a treatment with an acid-binding agent the dyestutf yields blue shades possessing excellent fastness to Wet treatments such as mild or severe washing, acid or alkali spotting, perspiration, and to light. Example 2 I In place of the 86.7 parts of the tetra-sodium salt of A N=N- N=N 8 7 the copper-containing aminodisazo compound used in Exl 'E ample 1 there are used 95.75 parts of the tetra-sodium Z salt of the copper-containing aminodisazo compound ob- 0:11) tained by coupling diazotised aniline-2:5-disulphonic acid with 2-methoxy-5-methylaniline, rediazotising, coupling wherein with 7-(fV-ammo-3'-sulphophenylam no) 1 naphthol- 40 A represents a radical selected from the class consistsulphornc acid under alkaline conditions and finally treating of sulphophenyl and sulphonaphthyl Iadicalls. ing the resulting aminodisazo compound with an aqueous and L which is attached to one of the 63 solutlon of cupramqlqmum Sulphate" positions of the naphthalene nucleus, represents a The copper-containing azo dyestutf so obtained, when group of the formula: applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent, yields grey shades possessing very good fastness to washing.

Example 3 NH-\ NH7CO-CH=CH2- Diazotised 2-aminonaphthalene-4:S-disulphonic acid is H coupled with the disodium salt of the N-methane w-sulphonate of Z-aminobenzoic acid in aqueous medium at a and P represents a Positive integer not exceeding H f 6,5, th resulting compound i h t d i h an Z represents a member selected from the class consistaqueous solution of sodium hydroxide to hydrolyse oft ing of hydrogen and methyl, provided that when m the N-methane w-sulphonate group, the resulting aminois 2,Zis hydrogen; azo compound is diazotised and coupled with 6-acryln and m each independently represent a positive inoylamino-1-naphthol-3-sulphonic acid in aqueous alkateger not exceeding 2. line medium- 2. The copper-containing azo dyestutf of the formula:

A mixture of 84.3 parts of the tetl'asodium salt of the so-obtained disazo compound, 2000 parts of water, 27.4

parts of crystalline copper sulphate and 27.2 parts of crystalline sodium acetate is stirred for 2 hours at a temperature between and C. The mixture is then cooled to 20 C., and the dyestufl which is precipitated is filtered otf and dried.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestufE yields bluish-red shades which possess excellent fastness to washing.

What we claim is: 1. The copper-containing azo dyestuii of the formula:

SOsH

3. The copper-containing azo dyestuff of the formula:

NH.C O CH==CH2 References Cited by the Examiner V 4. The copper-containing azo dyestuif of the formula: UNITED STATES PATENTS 3,038,893 6/ 1962 Andrew 260-453 5 3,057,673 10/1962 Mills et a1 260153 X OCu0 NH.COCH=CH: 3,057,844 10/:1962 Andrew et a1 2*60148 X I I 3,057,846 10/1962 Andrew et a1. 260-148 N=N N=N 3,183,909 5/1964 Riat 260--194 X g 03H (13113 SOSH OTHER REFERENCES 10 Wegmann, J.: TextilPraxis, October 1958, pp. 1056- A 1061.

CHARLES B. PARKER, Primary Examiner. 

1. THE COPPER-CONTAINING AZO DYESTUFF OF THE FORMULA: 